CN108997116A - A kind of fullerene acrylic acid derivative and its preparation method and application - Google Patents
A kind of fullerene acrylic acid derivative and its preparation method and application Download PDFInfo
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- C—CHEMISTRY; METALLURGY
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/36—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of amides of sulfonic acids
- C07C303/40—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of amides of sulfonic acids by reactions not involving the formation of sulfonamide groups
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- C07C311/48—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups having nitrogen atoms of sulfonamide groups further bound to another hetero atom
- C07C311/49—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups having nitrogen atoms of sulfonamide groups further bound to another hetero atom to nitrogen atoms
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- C07C69/533—Monocarboxylic acid esters having only one carbon-to-carbon double bond
- C07C69/54—Acrylic acid esters; Methacrylic acid esters
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Abstract
The invention discloses a kind of fullerene acrylic acid derivatives and its preparation method and application.The structure of heretofore described fullerene acrylic acid derivative is shown in formula I, not only simple synthetic method, also has the molecular shape and size similar with PCBM, when being individually used for preparing organic photovoltaic devices, shows the device performance to compare favourably with PCBM.In addition, heretofore described fullerene acrylic acid derivative, its important feature is characterized in containing polymerizable acrylate or acrylamide group, therefore the derivative can pass through heat treatment and lighting process, cause the polymerized in-situ of material, so as to solidify the microstructure of organic photovoltaic devices active layer, the high efficiency and high stability of battery device are kept.
Description
Technical field
The present invention relates to field of photovoltaic materials, and in particular to a kind of fullerene acrylic acid derivative and preparation method thereof and answers
With.
Background technique
Solar energy can be changed into the electric energy that the mankind are easy to use by photovoltaic cell, be effective use solar energy, solved people
One of the important channel of energy crisis and environmental pollution that class is faced.As one of solar power generation new technology, organic photovoltaic
The light property of device is soft, is suitble to the solution low cost processing technologys such as printing, ink-jet, printing, is also easy preparation large area and flexible device
Part, the extensive concern by scientific circles and industry.In recent years, with large quantities of high performance polymers and small molecule photovoltaic
The invention of material and boundary material comes out, and the efficiency of organic photovoltaic devices has breached 12%, illustrates its bright application
Prospect.Although this level of efficiency, there are also a certain distance, needs further to improve, have compared to crystal silicon photovoltaic cell
Machine photovoltaic technology it is practical with greater need for solving the problems, such as device stability.
The currently used active layer of organic photovoltaic devices is to be blended by two kinds of materials of donor and receptor into body heterojunction
Structure.Donor material is p-type semiconductor material, and system has offer electronics and transmit the ability in hole rich in electronics, and receptor
Material is n-type semiconductor, has the ability for receiving and transmitting electronics.Efficient photoelectric conversion requires both materials to want
The nanoscale micro phase separation structure of interpenetrating networks formula is formed, the width of each material phase is preferably kept in 20 nanoscales or less.But
It is, since strong interaction being not present between two kinds of material molecules, even if both materials are obtained more by various means
Ideal active layer structure, obtained structure are also metastable state thermodynamically, can be developed over time and gradually, to
Macroscopical phase separation structure development.Therefore, the evolution of organic photovoltaic devices active layer structure is the unstable important inherence of its device
Factor needs to obtain adequate solution.In order to solve this problem, scientist proposes that exploitation and use can post-crosslinking or rear polymerizations
Photovoltaic material prepare the strategy of battery device active layer.Using this strategy, ideal microstructure is obtained in active layer
Later, starting crosslinking or polymerization reaction, so as to the microstructure of curing activity layer, high degree inhibits the micro- of active layer
Structural evolution is seen, the stability of battery device is improved.
Due to being always with excellent electron acceptability and isotropic electron transport ability, fullerene derivate
The organic photovoltaic acceptor material haveing excellent performance.In particular, [6,6]-phenyl-fullerene-methyl butyrate (PCBM), including C60Spread out
Biological PC61BM and C70Derivative PC71BM is the Typical Representative in fullerene acceptor material, and photovoltaic performance is prominent, in field
In it is the most frequently used.Due to its global molecular form, PCBM molecule is very easy to migration in active layer, often it can be seen that active layer
Occur big aggregation under heat effect, device performance is caused to be decayed rapidly.Based on above-mentioned strategy, have some cross-linking or can
The fullerene derivate of polymerization is reported, such as J.Mater.Chem.2005,15,5158-5163；J.Am.Chem.Soc.2010,
132,4887-4893；J.Mater.Chem.C 2014,2,7163–7167；J.Mater.Chem.A 2015,3,21856-
21863..But cross-linking or polymerization the fullerene derivate of these work report, will substantially using PCBM as raw material
It is hydrolyzed into carboxylic acid derivates, then reacts with the reagent for carrying polymerizable functional group, and polymerizable functional group is introduced to fowler
Ene derivative assigns its polymerizable or crosslinkable property.But the fullerene that such MOLECULE DESIGN and synthetic method obtain
Derivative possesses the soluble side chain and molecular shape bigger than PCBM, when greatly having damaged it separately as acceptor material
Photovoltaic performance.
Summary of the invention
Technical problem to be solved by the present invention lies in order to overcome in the prior art with molecules such as PCBM and its derivatives
It is very easy to migration in active layer for the fullerene derivate class organic photovoltaic acceptor material of representative, often goes out under heat effect
Now big aggregation, leads to problems such as device performance decay rapidly；Or existing cross-linking or polymerization fullerene derivate
Possess the soluble side chain and molecular shape bigger than PCBM, greatly damages its photovoltaic performance separately as acceptor material when
The problems such as, thus provide a kind of fullerene acrylic acid derivative and its preparation method and application.Fullerene propylene of the invention
Acid derivative not only simple synthetic method, also has the molecular shape and size similar with PCBM, is individually used for preparing organic
When photovoltaic device, the device performance to compare favourably with PCBM is shown.In addition, heretofore described fullerene acrylic acid is derivative
Object, important feature is characterized in containing polymerizable acrylate or acrylamide group, therefore the derivative can pass through heat
Processing and lighting process, cause the polymerized in-situ of material, so as to solidify the microstructure of organic photovoltaic devices active layer, protect
Hold the high efficiency and high stability of battery device.
The present invention solves above-mentioned technical problem by following technical proposals.
The present invention provides a kind of fullerene acrylic acid derivative, structure is shown in formula I:
Wherein, CnFor the fullerene containing n carbon atom, n desirable 60,70,84 or 120；
(Ar)mFor the connected conjugation segment of m aromatic groups substituted or unsubstituted each independently, m is selected from 1-20's
Any integer, Ar are independently represented each other substituted or unsubstituted aryl or heteroaryl；The substituted or unsubstituted aryl
Or the substituent group in heteroaryl is each independently selected from C1-C40Alkyl, C1-C40Alkoxy, C1-C40Halogenated alkyl, C1-C40-C
(=O)-, C1-C40Alkylaryl, C1-C40Alkyl silicon alkynyl；
Z is-O- or-NH-；
R1、R2、R3、R4、R5And R6As the substituent group on carbon skeleton, it is each independently selected from hydrogen atom or C1-C40Alkane
Base；
Subscript x is selected from any integer of 1-20, represents-(Ar)mThe number of methylene between-Z-C (=O)-；
Subscript y is selected from any integer of 1-6, represents the fullerene CnThe number of the side chain of addition on sphere.
In the present invention, the silicon alkynyl is the base for being used to bring solubilizing effect in field of photovoltaic materials used in routine
, include silicon atom and acetylene bond in structure, specifically connects bonding mode and be not required to be particularly limited to.
In the present invention, when y is 1, shown in Formulas I representation be single addition fullerene derivate；When y is 2, institute
The Formulas I representation shown is the fullerene derivate of double additions；When y be 3-6 any integer when, shown in Formulas I representation
For the fullerene derivate added.
In the present invention, Ar is preferably monocyclic aryl or fused ring aryl each independently；The fused ring aryl is single by 2-7
Cyclophane base condenses derivative mutually and obtains, and monocyclic aryl therein may be the same or different.
Wherein, the monocyclic aryl is preferably selected from the group of following five yuan or hexa-atomic aryl:
In formula, Z1、Z2、Z3、Z4、Z5And Z6It is same or different to each other, the case where respectively meeting valence state and armaticity requires
Under, it is each independently selected from carbon, silicon, nitrogen, sulphur, oxygen, selenium or tellurium atom.
In the present invention, m is preferably 1.
In the present invention, Ar preferably following any monocyclic aryls:
Wherein, R7﹑ R8And R9It is same or different to each other, is each independently selected from hydrogen atom or C1-C40Alkyl.
In the present invention, CnIt is preferred that C60Or C70。
In the present invention, Z preferably-O-.
In the present invention, R1、R2、R3、R4、R5And R6It is preferably all hydrogen atom.
In the present invention, subscript x is preferably any integer of 2-10, further preferably 3,4,5,6,7,8 or 9.
In the present invention, subscript y preferably 1 or 2.
In the present invention, the further preferably following any compound of the fullerene acrylic acid derivative:
The present invention further additionally provides a kind of preparation method of fullerene derivate shown in formula I comprising following
Step: in organic solvent, in the presence of a base, the fullerene derivate intermediate as shown in Formula II and such as formula III
Shown in acryloyl chloride intermediate carry out condensation reaction as follows；
Wherein, the fullerene derivate intermediate as shown in Formula II and each substituent group in the acryloyl chloride as shown in formula III
Definition it is all as described above.
In the present invention, when Z is-O- in the fullerene derivate intermediate as shown in Formula II, the condensation reaction is
It uses the alcohol of organic field routine and acyl chlorides to be condensed to carry out for the mechanism of ester；When the fullerene derivate intermediate as shown in Formula II
When middle Z is-NH-, the condensation reaction is to use the amine of organic field routine and acyl chlorides to be condensed to carry out for the mechanism of amide.
In the present invention, the condensation reaction in the reaction environment used in the such reaction routine of organic synthesis field into
Row generally under the conditions of anhydrous and oxygen-free, and carries out system protection with inert gas such as argon gas or nitrogen.
In the present invention, the organic solvent can be the preferred ether of the present invention used in the such reaction routine of organic synthesis field
One of class, halogenated aryl hydrocarbon class and class containing enpara are a variety of, further preferred tetrahydrofuran, chlorobenzene, o-dichlorohenzene and chlorine
It is one of imitative or a variety of.
In the present invention, the dosage of the organic solvent can be the present invention used in the such reaction routine of organic synthesis field
It is preferred that the molar concentration of the fullerene derivate intermediate in the organic solvent as shown in Formula II is 0.13:
60mol/L。
In the present invention, the alkali can be preferred organic amine in the present invention used in the such reaction routine of organic synthesis field
Class such as triethylamine and/or inorganic base such as sodium carbonate, further preferred triethylamine.
In the present invention, the dosage of the alkali can be used in the such reaction routine of organic synthesis field, in the present invention preferably
The molar ratio of the alkali and the fullerene derivate intermediate as shown in Formula II is 51:1.
In the present invention, the dosage of the acryloyl chloride as shown in formula III can be normal for the such reaction of organic synthesis field
Used in rule, the preferably acryloyl chloride as shown in formula III and the fullerene as shown in Formula II is derivative in the present invention
The molar ratio of object intermediate is 50:1.
In the present invention, the reaction temperature of the condensation reaction can be used in the such reaction routine of organic synthesis field, originally
Invention preferable reaction temperature is -30~150 DEG C, further preferred 0~80 DEG C.
In the present invention, the preparation method of the fullerene derivate shown in formula I preferably includes following step: in nothing
Under water oxygen free condition, in argon atmosphere, the fullerene derivate intermediate shown in Formula II and the alkali are placed in as described in
Organic solvent in, the acryloyl chloride such as formula III shown in is added dropwise, drop is complete, reacts under the reaction temperature.
In the present invention, after the preparation method of the fullerene derivate shown in formula I preferably still further comprises
Reason process, the last handling process can be for used in the such reaction routine of organic synthesis field, present invention preferably comprises following steps
It is rapid: after the condensation reaction, be added water quenching reaction, washing three times, chloroform extraction three times, anhydrous sodium sulfate it is dry
Dry, rotary evaporation removes solvent.
In the present invention, the preparation method of the fullerene derivate shown in formula I preferably still further comprises product
Purification process, the product purification process can for used in the such reaction routine of organic synthesis field, the present invention preferably described in
Product purification process includes the following steps: that will post-process resulting product crude product passes through column chromatography chromatogram separating-purifying, eluant, eluent
Preferably methylene chloride/petroleum ether；Or include the following steps: through gel permeation chromatography (GPC) separating-purifying.
In the present invention, it is also preferable to include following steps for the preparation method of the fullerene derivate shown in formula I:
In organic solvent, in the presence of a base, the hydrazone class intermediate as shown in formula IV and fullerene CnIt carries out as follows
Addition reaction；
Wherein, the hydrazone class intermediate as shown in formula IV and the fullerene CnIn each substituent group definition institute as above
It states.
In the present invention, the addition reaction using the such reaction popular response condition of organic synthesis field and parameter into
Row.
In the present invention, the addition reaction in the reaction environment used in the such reaction routine of organic synthesis field into
Row generally under the conditions of anhydrous and oxygen-free, and carries out system protection with inert gas such as argon gas or nitrogen.
In the present invention, the organic solvent is the preferred pyridine of the present invention used in the such reaction routine of organic synthesis field.
In the present invention, the dosage of the organic solvent is used in the such reaction routine of organic synthesis field, and the present invention is excellent
The choosing molar concentration of the hydrazone class intermediate in the organic solvent as shown in formula IV is 1.8:30mol/L.
In the present invention, the alkali is used in the such reaction routine of organic synthesis field, and generally highly basic, the present invention are preferred
Sodium alkoxide and/or potassium alcoholate, further preferred sodium methoxide.
In the present invention, the dosage of the alkali is preferred institute in the present invention used in the such reaction routine of organic synthesis field
The molar ratio of the alkali and the hydrazone class intermediate as shown in formula IV stated is 1:1-1.5:1, such as 1.5:1.3.
In the present invention, the fullerene CnDosage be used in the such reaction routine of organic synthesis field, it is of the invention in
It is preferred that the fullerene CnMolar ratio with the hydrazone class intermediate as shown in formula IV is 0.5:1-1.5:1.
In the present invention, the fullerene CnSolution preferably participates in reacting with its solution form, further preferred fullerene Cn
Chlorinated solvents solution；The chlorinated solvents can select one of chlorobenzene, o-dichlorohenzene, chloroform or a variety of, preferably
Chlorobenzene and/or o-dichlorohenzene.
In the present invention, the reaction temperature of the addition reaction is this hair used in the such reaction routine of organic synthesis field
Bright preferred room temperature is to 200 DEG C, and further preferred 50~150 DEG C.
In the present invention, it is also preferable to include following steps for the preparation method of the fullerene derivate shown in formula I:
Under the conditions of anhydrous and oxygen-free, in argon atmosphere, the hydrazone class intermediate shown in formula IV is placed in as described in organic solvent in, be added
The alkali adds fullerene C after room temperature processingnChlorinated solvents solution, reacted under the reaction temperature, i.e.,
It can.
In the present invention, after the preparation method of the fullerene derivate shown in formula I preferably still further comprises
Reason process, the last handling process can be for used in the such reaction routine of organic synthesis field, present invention preferably comprises following steps
Rapid: after the addition reaction, vacuum distillation removes solvent.
In the present invention, the preparation method of the fullerene derivate shown in formula I preferably still further comprises product
Purification process, the product purification process can for used in the such reaction routine of organic synthesis field, the present invention preferably described in
Product purification process includes the following steps: to post-process gained crude product by column chromatography chromatogram separating-purifying, respectively using elution
Agent carbon disulfide, methylene chloride, chloroform/methanol separate product.
In the present invention, it is also preferable to include following steps for the preparation method of the fullerene derivate shown in formula I:
In organic solvent, by ketone compounds shown as a formula V and to Methyl benzenesulfonyl hydrazine (TsNHNH2) carry out condensation reaction；
Wherein, in ketone compounds shown as a formula V and the hydrazone class intermediate as shown in formula IV each substituent group
It defines all as described above.
In the present invention, the condensation reaction using the such reaction popular response condition of organic synthesis field and parameter into
Row.
In the present invention, the condensation reaction in the reaction environment used in the such reaction routine of organic synthesis field into
Row generally under the conditions of anhydrous and oxygen-free, and carries out system protection with inert gas such as argon gas or nitrogen.
In the present invention, the organic solvent is used in the such condensation reaction routine of organic synthesis field, and the present invention is preferred
Alcohols and/or ether solvent, one of the further preferred methanol of the alcohols solvent, ethyl alcohol and isopropanol or a variety of.
In the present invention, the dosage of the organic solvent is used in the such reaction routine of organic synthesis field, and the present invention is excellent
Molar concentration of the choosing ketone compounds shown as a formula V in the organic solvent is 0.05mol/L.
It is described to Methyl benzenesulfonyl hydrazine (TsNHNH in the present invention2) dosage be that the such reaction of organic synthesis field is normal
It is preferably described to Methyl benzenesulfonyl hydrazine (TsNHNH in the present invention used in rule2) and the ketone compounds shown as a formula V
Molar ratio be 1:1-2:1.
In the present invention, the condensation reaction preferably can also be added catalyst and promote reaction, and the catalyst is organic
Used in the such reaction routine in synthesis field, preferred bronsted acid in the present invention, further preferred organic acid such as acetic acid and/or nothing
Machine acid such as sulfuric acid.
In the present invention, the dosage of the bronsted acid is used in the such reaction routine of organic synthesis field, and is not required to
It is particularly limited to, the molar ratio of bronsted acid preferably described and the ketone compounds shown as a formula V in the present invention
0.005:1-0.1:1。
In the present invention, the reaction temperature of the condensation reaction is this hair used in the such reaction routine of organic synthesis field
Bright preferred room temperature is to 200 DEG C, the atmospheric pressure reflux temperature of the further preferably described organic solvent.
In the present invention, it is also preferable to include following steps for the preparation method of the fullerene derivate shown in formula I:
Under the conditions of anhydrous and oxygen-free, in argon atmosphere, by ketone compounds shown as a formula V and to Methyl benzenesulfonyl hydrazine (TsNHNH2)
Condensation reaction is carried out under the reaction temperature；If reaction system is there is also catalyst, the catalyst can be with it
He directly mixes reaction mass, and each material addition sequence is not required to be particularly limited in reaction system.
In the present invention, after the preparation method of the fullerene derivate shown in formula I preferably still further comprises
Reason process, the last handling process can be for used in the such reaction routine of organic synthesis field, present invention preferably comprises following steps
Rapid: after the condensation reaction, concentration removes solvent.
In the present invention, the preparation method of the fullerene derivate shown in formula I preferably still further comprises product
Purification process, the product purification process can for used in the such reaction routine of organic synthesis field, the present invention preferably described in
Product purification process includes the following steps: will to post-process gained crude product and is separated by column chromatography chromatogram, eluant, eluent for ethyl acetate/
Petroleum ether.
In the present invention, the ketone compounds shown as a formula V can be used this field customary preparation methods and be prepared.
The present invention still further provides each compound as shown in Formula II, III or IV:
The present invention still further provides a kind of preparation method of fullerene derivate intermediate as shown in Formula II, packet
Include following steps: in organic solvent, in the presence of a base, the hydrazone class intermediate as shown in formula IV and fullerene CnInto
Row addition reaction；
Wherein, the hydrazone class intermediate as shown in formula IV and the fullerene CnIn each substituent group definition institute as above
It states.
Wherein, each reaction condition of the addition reaction and parameter are as previously described.
The present invention still further provides a kind of preparation method of hydrazone class intermediate as shown in formula IV comprising Xia Shubu
It is rapid: in organic solvent, by ketone compounds shown as a formula V and to Methyl benzenesulfonyl hydrazine (TsNHNH2) condensation reaction is carried out,
?；
Wherein, in ketone compounds shown as a formula V and the hydrazone class intermediate as shown in formula IV each substituent group
It defines all as described above.
Wherein, each reaction condition of the condensation reaction and parameter are as previously described.
The present invention still further provides one kind fullerene acrylic acid derivative shown in formula I as organic photovoltaic battery
Acceptor material preparing the application in organic photovoltaic devices.
On the basis of common knowledge of the art, above-mentioned each optimum condition, can any combination to get each preferable reality of the present invention
Example.
The reagents and materials used in the present invention are commercially available.
The positive effect of the present invention is that:
1, polymerizable fullerene acrylic acid derivative of the invention not only simple synthetic method also has suitable with PCBM
Molecular shape and size, when being individually used for preparing organic photovoltaic devices, show the device performance to compare favourably with PCBM；
2, acrylate or acrylamide group that polymerizable fullerene acrylic acid derivative of the invention carries, very
It is easy to cause polymerization by the conditions such as heat, illumination, so that the fullerene compound of small molecule is changed into gathering for line style or crosslinking
Object is closed, the microstructure of curing activity layer improves the efficiency and stability of battery device；
3, the development and application of polymerizable fullerene acrylic acid derivative of the invention, be expected to obtain have both high efficiency and
The organic photovoltaic devices of high stability push the functionization of organic photovoltaic technology.
Detailed description of the invention
Fig. 1 is compound PC61PrA、PC61BA、PC61PeA and PC61The ultraviolet-visible absorption spectra figure of BM chloroformic solution.
Fig. 2 is compound PC61PrA、PC61BA、PC61PeA and PC61Cyclic voltammetry curve of the BM at current potential (- 2.0~0)
Figure.
Fig. 3 is compound PC61PrA、PC61BA、PC61PeA and PC61Cyclic voltammetry curve of the BM at current potential (0~2.0)
Figure.
Fig. 4 is based on P3HT/PC61BA、P3HT/PC61The current -voltage curve of BM solar battery.
Fig. 5 is P3HT/PC61BA and P3HT/PC61The variation of BM solar cell device heat treatment efficiency at 150 DEG C is bent
Line.
Specific embodiment
The present invention is further illustrated below by the mode of embodiment, but does not therefore limit the present invention to the reality
It applies among a range.In the following examples, the experimental methods for specific conditions are not specified, according to conventional methods and conditions, or according to quotient
The selection of product specification.It should be understood that within the scope of the present invention, above-mentioned each technical characteristic of the invention and below (such as embodiment)
It can be combined with each other between each technical characteristic of middle specific descriptions, to form a new or preferred technical solution.It is limited to a piece
Width, not repeated them here.
In the following examples, the experimental methods for specific conditions are not specified, usually according to normal condition or according to institute of manufacturer
It is recommended that condition.Unless otherwise stated, otherwise percentage and number are calculated by weight.Unless otherwise defined, as used herein
All professional and scientific terms have the same meanings as commonly understood by one of ordinary skill in the art.In addition, any similar to described content
Or impartial method and material can be applied to the method for the present invention.Preferred implement methods and materials described in the text only present a demonstration
It is used.
Embodiment 1:[6,6]-phenyl-C61-butyl acrylate(PC61BA synthesis)
(1) synthesis of 5- hydroxyl -1- phenyl pentanone Tosylhydrazone
0.64g compound 4-hydroxy base -1- is added to the there-necked flask of 50mL under argon atmosphere in the processing of device anhydrous and oxygen-free
Phenyl butanone (3.6mmol, 1eq) and 0.66g unifor (3.6mmol, 1eq).The steamed methanol of 20mL weight is added to
In reaction flask, stop reaction after reacting 6h at reflux, separated after concentration by column chromatography chromatogram, eluant, eluent is acetic acid second
Ester/petroleum ether=2:3 (v:v) obtains 0.94g 5- hydroxyl -1- phenyl pentanone Tosylhydrazone, yield 75%.
(2) cycloaddition reaction prepares fullerene derivate
0.62g compound 5- hydroxyl -1- is added into 250mL there-necked flask under argon atmosphere for the processing of device anhydrous and oxygen-free
Phenyl pentanone Tosylhydrazone (1.8mmol, 1.3eq), 0.11g sodium methoxide (2.0mmol, 1.5eq) and heavy steamed pyridine
30mL reacts at room temperature 20min.1g C60(1.38mmol, 1eq) is dissolved in ultrasound in the steamed o-dichlorohenzene solvent of 150mL weight
20min, the C that ultrasound is crossed60O-dichlorobenzene solution be added in reaction flask, react 48h under counterflow condition.It is sharp after reaction
Solvent is removed with vacuum distillation, by column chromatography chromatogram separating-purifying, eluant, eluent elutes unreacted when being carbon disulfide
C60, methylene chloride as eluant, eluent elute PC61BOH, chloroform/methanol elute the by-product added as eluant, eluent, most
After respectively obtain the unreacted C of 0.51g60、0.45g PC61The yield of the by-product that BOH and 0.33g add, target product is
45%.
1H NMR(400MHz,CDCl3/CS2, ppm): δ 7.93 (d, J=8Hz, 2H), 7.54 (t, J=6Hz, 2H), 7.45
(t, J=8Hz, 1H), 3.74 (t, J=8Hz, 2H), 2.91 (t, J=8Hz, 2H), 1.90-1.98 (m, 2H), 1.74-1.82
(m,2H).
(3) acroleic acid esterification reacts
The processing of device anhydrous and oxygen-free, under argon atmosphere, is added 0.12gPC into the there-necked flask of 100mL61BOH
The chloroform that (0.13mmol, 1eq), 0.92mL triethylamine (6.63mmol, 51eq) and 60mL steam again.It, will under the conditions of ice-water bath
0.54mL acryloyl chloride (6.49mmol, 50eq) is slowly dropped in reaction flask, and 3h is reacted at room temperature after completion of dropwise addition.Reaction terminates
Be added water quenching reaction afterwards, washing three times, chloroform extraction it is dry with anhydrous sodium sulfate afterwards three times, rotary evaporation removes solvent.It is logical
Column chromatography chromatogram separating-purifying is crossed, eluant, eluent is that methylene chloride/petroleum ether=1:1 (v:v) obtains product 74.5mg, and yield is
65%.
1H NMR(400MHz,CDCl3, ppm): δ 7.93 (d, J=8Hz, 2H), 7.54 (t, J=6Hz, 2H), 7.47 (t, J
=6Hz, 1H), 6.31 (dd, J1=16Hz, J2=20Hz, 1H), 6.1 (dd, J1=J2=12Hz, 1H), 5.81 (dd, J1=J2
=12Hz, J2=8Hz, 1H), 4.24 (t, J=8Hz, 2H), 2.89-2.93 (m, 2H), 1.88-1.95 (m, 2H)13C NMR
(100MHz,CDCl3,ppm):δ166.22,147.89,145.09,144.38,142.91,140.72,138.00,137.53,
136.90,132.09,130.70,128.39,128.35,128.17,89.00,64.12,52.16,33.80,29.70,
28.47,23.43.MALDI FT-MS:m/z 936.1143(M+).
Embodiment 2:[6,6]-phenyl-C61-propyl acrylate(PC61PrA synthesis)
(1) synthesis of 4- hydroxyl -1- phenyl butanone Tosylhydrazone
Synthetic method is with 5- hydroxyl -1- phenyl pentanone Tosylhydrazone, the difference is that 4- hydroxyl -1- phenyl butanone
Substitute 5- hydroxyl -1- phenyl pentanone and tolysulfonyl hydrazine reaction.After reaction most of solvent rotary evaporation is fallen to obtain
Concentrate is stood overnight precipitation white solid by concentrate in refrigerator, filters out white crystal, and wash one with cold methanol
Secondary, normal-temperature vacuum is dried to obtain product 2.9g, yield 80%.
(2) cycloaddition reaction prepares fullerene derivate
The same PC of synthetic method61BOH, the difference is that 4- hydroxyl -1- phenyl butanone Tosylhydrazone is substituted 5- hydroxyl
Base -1- phenyl pentanone Tosylhydrazone.Finally respectively obtain the unreacted C of 0.42g60、0.45g PC61PrOH and 0.2g are more
The by-product of addition, the yield of target product are 45%.
1H NMR(400MHz,CDCl3, ppm): δ 7.94 (d, J=8Hz, 2H), 7.55 (q, J=8Hz, 2H), 7.45 (t, J
=8Hz, 2H), 3.84 (t, J=8Hz, 2H), 2.95-2.99 (m, 2H), 2.10-2.17 (m, 2H)
(3)PC61The synthesis of PrA molecule
The same PC of method61The synthesis of BA, the difference is that by PC61PrOH substitutes PC61BOH finally obtains crude product
86mg, thick yield are 71%, are further purified by GPC and finally obtain 72mg product, yield 60%.
1H NMR(400MHz,CDCl3, ppm): δ 7.93 (d, J=8Hz, 2H), 7.56 (t, J=6Hz, 2H), 7.48 (t, J
=6Hz, 1H), 6.40 (dd, J1=J2=8Hz, 1H), 6.11 (dd, J1=J2=8Hz, 1H), 5.81 (dd, J1=J2=4Hz,
1H), 4.35 (t, J=4Hz, 2H), 2.97-3.00 (m, 2H), 2.21-2.27 (m, 2H)13C NMR(100MHz,CDCl3,
ppm):δ161.30,143.86,142.85,140.21,138.91,138.14,137.32,135.90,133.17,132.73,
131.84,127.19,126.10,123.64,123.45,75.02,59.09,46.75,26.03,21.57.MALDI FT-MS:
m/z 922.0988(M+).
Embodiment 3:[6,6]-phenyl-C61-pentyl acrylate(PC61PeA synthesis)
(1) synthesis of 6- hydroxyl -1- phenyl hexanone Tosylhydrazone
Synthetic method with 5- hydroxyl -1- phenyl pentanone Tosylhydrazone synthesis, the difference is that 6- hydroxyl -1- benzene
Base hexanone substitutes 5- hydroxyl -1- phenyl pentanone and tolysulfonyl hydrazine reaction.Finally obtain product 3.15g, yield 80%.
(2)PC61The synthesis of PeOH molecule
Method with PCBOH synthesis, the difference is that by 6- hydroxyl -1- phenyl hexanone Tosylhydrazone substitute 5- hydroxyl
Base -1- phenyl pentanone Tosylhydrazone and C60Reaction.Finally respectively obtain the unreacted C of 0.75g60、0.85g PC61PeOH
The by-product added with 0.38g, the yield of target product are 45%.
1H NMR(400MHz,CDCl3/CS2, ppm): δ 7.88 (d, J=6.9Hz, 2H), 7.49 (t, J=7.4Hz, 2H),
7.43 (t, J=7.4Hz 1H), 3.64 (t, J=6.3Hz, 2H), 2.81-2.87 (m, 2H), 1.84-1.88 (m, 2H), 1.60-
1.65(m,2H).1.55-1.56(m,2H).
(3)PC61The synthesis of PeA molecule
The same PC of synthetic method61The synthesis of BA, the difference is that by PC61PeOH substitutes PC61BOH and acryloyl chloride reaction,
Finally obtain product 21mg, yield 47%.
1H NMR(400MHz,CDCl3, ppm): δ 7.92 (d, J=6.8Hz 2H), 7.54 (t, J=6.2Hz 2H), 7.46
(t, J=5.9Hz 1H), 6.39 (dd, J1=1.1Hz, J2=13.9Hz, 1H), 6.10 (dd, J1=8.3Hz, J2=13.9Hz,
1H),5.82(dd,J1=1.1Hz, J2=8.4Hz, 1H), 4.18 (t, J=5.3Hz, 2H), 2.87-2.90 (m, 2H), 1.87-
1.92(m,2H).1.75-1.79(m,2H).1.58-1.62(m,2H).13C NMR(100MHz,CDCl3,ppm):δ166.44,
149.10,148.18,145.34,144.64,143.28,143.14,142.43,142.26,141.15,140.88,138.17,
137.67,137.24,132.26,130.77,128.68,128.48,128.28,8.29,64.65,52.50,34.38,
28.78,26.88,26.30.MALDI FT-MS:m/z 950.1300(M+).
Embodiment 4:[6,6]-phenyl-C71-propyl acrylate(PC71PrA synthesis)
(1)PC71The synthesis of PrOH molecule
The same PC of synthetic method61PrOH fullerene derivate, the difference is that utilizing C in raw material70Substitute C60With 4- hydroxyl
Base -1- phenyl butanone tolysulfonyl hydrazone reaction, yield 25%.
(2)PC71The synthesis of PrA
The same PC of synthetic method61PrA fullerene derivate, the difference is that utilizing PC in raw material71PrOH substitution
PC61PrOH and 4- hydroxyl -1- phenyl butanone tolysulfonyl hydrazone reaction, yield 30%.
1H NMR(400MHz,CDCl3,ppm):δ7.94(2H),7.52(2H),7.44(1H),3.81(2H),2.53
(2H),2.04(2H).
Embodiment 5: the characterization of fullerene derivate performance
The characterization of ultraviolet-visible absorption spectroscopy: fullerene derivate is dissolved in chloroform, is configured to 10-5mol/L
Solution, test the uv-vis spectra of fullerene derivate solution state, surveyed spectrogram is listed in Fig. 1.The result shows that compound
PC61PrA、PC61BA、PC61PeA and PC61The light abstraction width of BM is similar, 329nm, 431nm, 490nm (weaker, wider)
And have identical absorption peak at 690nm.Importantly, they have identical initial absorption peak at 710nm, this illustrates them
Possess identical optical band gap 1.74eV.These are statistics indicate that the fullerene derivate invented has and PC61BM the same suction
Receive range and intensity.
The characterization of electrochemical properties: Ag/AgNO is used3Electrode makees reference electrode, Pt electrode makees auxiliary electrode, glass-carbon electrode
Make working electrode, ferrocene (Fc) is swept as reference in o-dichlorohenzene/acetonitrile in the mixed solvent with the speed of 50mV/s
It retouches, to PC61PrA、PC61BA、PC61PeA and PC61The electrochemical properties of BM are tested, and surveyed spectrogram is listed in Fig. 2 and Fig. 3.It surveys
The initial oxidation current potential E of examination gained ferroceneFc/Fc+For 0.17eV.According to formula: LUMO=- (Ere,onset-EFc/Fc++4.8)eV
And HOMO=- (Eox,onset-EFc/Fc++ 4.8) eV calculates their HOMO and lumo energy, is listed in table 1.
1 compound PC of table61PrA、PC61BA、PC61PeA and PC61The basic performance of BM
Resulting polymerizable fullerene derivate PC seen from table 161PrA、PC61BA、PC61PeA and PC61BM has almost
The same HOMO energy level and lumo energy.
The characterization of aggregation property: by PC61In BA drop coating to glass plate, after heating 1h at 150 DEG C, washed away with chloroform solvable
The part of solution, as a result, it has been found that, there is 63.5% substance to remain on a glass.This shows that PC61BA has cross-linking rear curability
Matter.
Embodiment 6: the preparation and characterization of the organic solar batteries based on polymerizable fullerene derivate
The battery device structure of organic solar uses ITO/PEDOT:PSS/ active layer/Ca/Al, and wherein active layer is by gathering
(3- hexyl thiophene) (P3HT) and PC61BA (weight ratio 1:1) is blended.Preparation flow are as follows: in clean ITO electro-conductive glass
On, then spin coating (4000rpm) PEDOT:PSS aqueous solution is heat-treated 15min at 150 DEG C and forms PEDOT:PSS conductive layer,
Then in N2(O2 < 1ppm, H in the glove box environment of atmosphere2O < 1ppm), the P3HT/PC that will have been prepared61The chlorobenzene solution of BA revolves
It is coated on PEDOT:PSS layer.After through 150 DEG C of heat treatment 1h carry out polymerizing curables, 10-6Ca and Al is deposited under the vacuum of mbar
Electrode completes the preparation of battery.Finally, battery is placed in the light of AAA sunlight simulation system (Oriel 94043A, 450W) offer
Strong 100mW cm-2Illumination under, its current -voltage curve (J-V) is tested by 2420 source table of Keithley, characterizes device performance.
Under similarity condition, preparation is based on P3HT/PC61The solar battery of BM tests its J-V curve.The J-V curve column of two devices
In Fig. 4, basic device parameter is listed in table 2.These statistics indicate that, be based on P3HT/PC61The device and P3HT/PC of BA61BM is suitable.
Table 2 is based on P3HT/PC61BA and P3HT/PC61The device parameters of BM solar battery
These statistics indicate that, be based on P3HT/PC61The device and P3HT/PC of BA61BM is suitable.
Two devices are placed at 150 DEG C and are heat-treated different time, test the variation of the incident photon-to-electron conversion efficiency of device, as a result
It is listed in Fig. 5.There it can be seen that device P3HT/PC61The thermal stability of BA efficiency will be significantly better than reference device P3HT/
PC61BM.After heating 35h at 150 DEG C, P3HT/PC61BA device is maintained essentially at the 80% of highest level, and P3HT/
PC61The efficiency of BM device drops to 40% of its highest level or so.
All references mentioned in the present invention is incorporated herein by reference, independent just as each document
It is incorporated as with reference to such.In addition, it should also be understood that, after reading the above teachings of the present invention, those skilled in the art can
To make various changes or modifications to the present invention, such equivalent forms equally fall within model defined by the application the appended claims
It encloses.
Claims (11)
1. a kind of fullerene acrylic acid derivative, which is characterized in that its structure is shown in formula I:
Wherein, CnFor the fullerene containing n carbon atom, n 60,70,84 or 120；
(Ar)mFor the connected conjugation segment of m aromatic groups substituted or unsubstituted each independently, m is selected from any whole of 1-20
Number, Ar are independently represented each other substituted or unsubstituted aryl or heteroaryl；The substituted or unsubstituted aryl or heteroaryl
Substituent group in base is each independently selected from C1-C40Alkyl, C1-C40Alkoxy, C1-C40Halogenated alkyl, C1-C40- C (=O)-,
C1-C40Alkylaryl, C1-C40Alkyl silicon alkynyl；
Z is-O- or-NH-；
R1、R2、R3、R4、R5And R6It is each independently selected from hydrogen atom or C1-C40Alkyl；
Subscript x is selected from any integer of 1-20；
Subscript y is selected from any integer of 1-6.
2. fullerene acrylic acid derivative as described in claim 1, which is characterized in that wherein,
When y is 1, shown in Formulas I representation be single addition fullerene derivate；
When y is 2, shown in Formulas I representation be double additions fullerene derivate；
When y be 3-6 any integer when, shown in Formulas I representation be the fullerene derivate added.
3. fullerene acrylic acid derivative as described in claim 1, which is characterized in that wherein,
Ar is each independently monocyclic aryl or fused ring aryl；The fused ring aryl is condensed mutually by 2-7 monocyclic aryl spreads out
It gives birth to and obtains, monocyclic aryl therein may be the same or different.
4. fullerene acrylic acid derivative as claimed in claim 3, which is characterized in that wherein,
The monocyclic aryl is selected from the group of following five yuan or hexa-atomic aryl:
In formula, Z1、Z2、Z3、Z4、Z5And Z6It is same or different to each other, it is former to be each independently selected from carbon, silicon, nitrogen, sulphur, oxygen, selenium or tellurium
Son.
5. fullerene acrylic acid derivative according to any one of claims 1-4, which is characterized in that wherein,
M is 1；
And/or Ar is each independently selected from following any monocyclic aryls:
Wherein, R7﹑ R8And R9It is same or different to each other, is each independently selected from hydrogen atom or C1-C40Alkyl；
And/or CnFor C60Or C70；
And/or Z is-O-；
And/or R1、R2、R3、R4、R5And R6It is hydrogen atom；
And/or subscript x is any integer of 2-10, preferably 3,4,5,6,7,8 or 9；
And/or subscript y is 1 or 2.
6. fullerene acrylic acid derivative as described in claim 1 is following any compound:
7. a kind of preparation method of fullerene derivate as claimed in any one of claims 1 to 6, which is characterized in that under it includes
State step: in organic solvent, in the presence of a base, the fullerene derivate intermediate as shown in Formula II with such as formula
Acryloyl chloride intermediate shown in III carries out condensation reaction as follows；
Wherein, the fullerene derivate intermediate as shown in Formula II and substituent group each in the acryloyl chloride as shown in formula III are determined
Justice is as described in claim any one of 1-6；
Wherein, one of the preferred ethers of the organic solvent, halogenated aryl hydrocarbon class and class containing enpara or a variety of, it is further excellent
Select one of tetrahydrofuran, chlorobenzene, o-dichlorohenzene and chloroform or a variety of；
Wherein, the molar concentration of the fullerene derivate intermediate in the organic solvent as shown in Formula II is preferred
For 0.13:60mol/L；
Wherein, the preferred organic amine of the alkali and/or inorganic base, further preferred triethylamine；
Wherein, the molar ratio of the alkali and the fullerene derivate intermediate as shown in Formula II is preferably 51:1；
Wherein, the acryloyl chloride as shown in formula III and the fullerene derivate intermediate as shown in Formula II
Molar ratio is preferably 50:1；
Wherein, the reaction temperature of the condensation reaction is preferably -30~150 DEG C, further preferred 0~80 DEG C.
8. preparation method as claimed in claim 7, which is characterized in that the preparation method further comprises following step:
In organic solvent, in the presence of a base, the hydrazone class intermediate as shown in formula IV and fullerene CnIt carries out as follows
Addition reaction；
Wherein, the hydrazone class intermediate as shown in formula IV and the fullerene CnIn each substituent group definition such as claim 1-6
Described in any one；
Wherein, the preferred pyridine of the organic solvent；
Wherein, the molar concentration of the hydrazone class intermediate in the organic solvent as shown in formula IV is preferably 1.8:
30mol/L；
Wherein, the preferred sodium alkoxide of the alkali and/or potassium alcoholate, further preferred sodium methoxide；
Wherein, the molar ratio of the alkali and the hydrazone class intermediate as shown in formula IV is preferably 1:1-1.5:1, and such as 1.5:
1.3；
Wherein, the fullerene CnMolar ratio with the hydrazone class intermediate as shown in formula IV is preferably 0.5:1-1.5:
1；
Wherein, the fullerene CnSolution preferably participates in reacting with its solution form, further preferred fullerene CnContaining chlorine it is molten
The solution of agent；The chlorinated solvents are one of chlorobenzene, o-dichlorohenzene and chloroform or a variety of, preferably chlorobenzene and/or neighbour two
Chlorobenzene；
Wherein, the preferred room temperature of the reaction temperature of the addition reaction is to 200 DEG C, and further preferred 50~150 DEG C.
9. preparation method as claimed in claim 8, which is characterized in that the preparation method further comprises following step:
In organic solvent, ketone compounds shown as a formula V are subjected to condensation reaction with to Methyl benzenesulfonyl hydrazine；
Wherein, the definition of ketone compounds shown as a formula V and each substituent group in the hydrazone class intermediate as shown in formula IV
As described in claim any one of 1-6；
Wherein, the preferred alcohols of the organic solvent and/or ether solvent, the further preferred methanol of the alcohols solvent, second
One of pure and mild isopropanol is a variety of；
Wherein, molar concentration of the ketone compounds shown as a formula V in the organic solvent is preferably
0.05mol/L；
Wherein, the molar ratio to Methyl benzenesulfonyl hydrazine and the ketone compounds shown as a formula V is preferably 1:1-
2:1；
Wherein, the condensation reaction is preferably additionally added catalyst and promotes to react, the preferred bronsted acid of the catalyst, into
The preferred organic acid of one step such as acetic acid and/or inorganic acid such as sulfuric acid；Wherein, the bronsted acid with it is described shown as a formula V
The molar ratios of ketone compounds be preferably 0.005:1-0.1:1；
Wherein, the preferred room temperature of the reaction temperature of the condensation reaction is to 200 DEG C, the further preferably described organic solvent it is normal
Press reflux temperature.
10. a kind of compound each as shown in Formula II, III or IV:
Wherein, the definition of each substituent group is as described in claim any one of 1-6.
11. a kind of receptor of fullerene acrylic acid derivative as claimed in any one of claims 1 to 6 as organic photovoltaic battery
Material is preparing the application in organic photovoltaic devices.
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| CN110818594A (en) * | 2019-11-27 | 2020-02-21 | 宁波卢米蓝新材料有限公司 | Fullerene derivative, application thereof and OLED (organic light emitting diode) device comprising fullerene derivative |
| CN111384245A (en) * | 2018-12-27 | 2020-07-07 | Tcl集团股份有限公司 | Composite material, preparation method thereof and quantum dot light-emitting diode |
| CN114384759A (en) * | 2021-12-16 | 2022-04-22 | 江苏博砚电子科技有限公司 | Florenol acrylate for black matrix photoresist, preparation method thereof, resin composition and application method |
-
2017
- 2017-06-07 CN CN201710424108.7A patent/CN108997116A/en active Pending
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| Title |
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| JIN-LONG WANG, ET AL.: ""An acrylated fullerene derivative for efficient and thermally stable polymer solar cells"", 《TETRAHEDRON LETTERS》 * |
| YANG BAI, ET AL.: ""Polymerizable C70 derivatives with acrylate functionality for efficient and stable solar cells"", 《TETRAHEDRON》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111384245A (en) * | 2018-12-27 | 2020-07-07 | Tcl集团股份有限公司 | Composite material, preparation method thereof and quantum dot light-emitting diode |
| CN110818594A (en) * | 2019-11-27 | 2020-02-21 | 宁波卢米蓝新材料有限公司 | Fullerene derivative, application thereof and OLED (organic light emitting diode) device comprising fullerene derivative |
| CN110818594B (en) * | 2019-11-27 | 2023-01-13 | 宁波卢米蓝新材料有限公司 | Fullerene derivative, application thereof and OLED (organic light emitting diode) device comprising fullerene derivative |
| CN114384759A (en) * | 2021-12-16 | 2022-04-22 | 江苏博砚电子科技有限公司 | Florenol acrylate for black matrix photoresist, preparation method thereof, resin composition and application method |
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